1-D helical chain, 2-D layered network and 3-D porous lanthanide-organic frameworks based on multiple coordination sites of benzimidazole-5,6- dicarboxylic acid: Synthesis, crystal structure, photoluminescence and thermal stability
Ping Wang, Rui Qing Fan, Yu Lin Yang, Xin Rong Liu, Peng Xiao, Xin Yu Li, Wuliji Hasi, Wen Wu Cao
Center for Computational Mathematics and Applications (CCMA)
One-dimensional to three-dimensional lanthanide coordination polymers 1-8 based on benzimidazole-5,6-dicarboxylic acid (H3BIDC) have been synthesized under hydrothermal conditions at different pH values, generally formulated as {[Pr(HBIDC)(ox)0.5(H2O)]·H 2O}n (1), [Yb(HBIDC)(ox)0.5(H 2O)2]n (2), and [Ln(HBIDC)(ox) 0.5(H2O)3]n [Ln = Ho (3), and Tb (4)] and {[Ln(H2BIDC)(HBIDC)(H2O)3] ·3H2O}n [Ln = Tb (5), Sm (6), Dy (7), and Gd (8), H2ox = oxalic acid]. All coordination polymers have been characterized by elemental analysis, infrared spectra and single-crystal X-ray diffraction. The structural diversity, luminescence and thermal properties of all coordination polymers have been investigated. Coordination polymers 1-8 exhibit four different structural types: topological analysis has given the 3-D pcu network, with the point symbol of {412·63} in coordination polymer 1. Coordination polymer 2 exhibits a 4-connected 4 4 topology, and coordination polymers 3-4 appear as 2-D (6,3)-connected hcb network topology. The 1-D helical infinite chain of coordination polymers 5-8 around the crystallographic 21 axis spread along the b axis direction, with different 1-D helical infinite chains forming 3-D supramolecular framework via hydrogen bonds and π-π stacking interactions. The coordination polymers 4 and 5 could be triggered to have intense characteristic lanthanide-centered green luminescence under UV excitation in the solid state at room and liquid nitrogen temperature, or dispersed in CH2Cl2 at 77 K. In coordination polymers 4 and 5, the oxalic acid introduced into coordination polymer 4 as a second ligand further sensitized the trivalent terbium ion, and resulted in longer fluorescence lifetimes of coordination polymer 4 (1058.58 μs at 298 K, 679.42 μs at 77 K in the solid-state, 867.82 μs in CH2Cl2 at 77 K) than coordination polymer 5 (595.06 μs at 298 K, 583.19 μs at 77 K in the solid-state, 584.38 μs in CH2Cl2 at 77 K). In coordination polymers 6 and 7, we not only measured emission spectra in the visible region, but also detected the infrequent NIR emission spectra in the near infrared region of samarium and dysprosium ions. The singlet excited state (30 303 cm-1) and the lowest triplet state energy level (24 390 cm-1) of H3BIDC ligand were calculated based on the UV-vis absorbance edges of ligand and the phosphorescence spectrum of Gd(iii) coordination polymer (8) at 77 K, showing that the effective extent of energy transfer from H3BIDC ligand to lanthanide ions follows the sequence of Tb3+, Dy3+ > Sm3+. Finally, thermal behaviors of all coordination polymers were studied by thermogravimetric analysis, which exhibited high thermal stability.
CrystEngComm
https://doi.org/10.1039/c3ce40184g
Published - Jun 14 2013
10.1039/c3ce40184g
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coordination polymers Physics & Astronomy 100%
dicarboxylic acids Physics & Astronomy 99%
Photoluminescence Engineering & Materials Science 94%
Rare earth elements Engineering & Materials Science 81%
Dicarboxylic Acid Chemical Compounds 62%
Thermodynamic stability Engineering & Materials Science 60%
Acids Engineering & Materials Science 53%
Wang, P., Fan, R. Q., Yang, Y. L., Liu, X. R., Xiao, P., Li, X. Y., Hasi, W., & Cao, W. W. (2013). 1-D helical chain, 2-D layered network and 3-D porous lanthanide-organic frameworks based on multiple coordination sites of benzimidazole-5,6- dicarboxylic acid: Synthesis, crystal structure, photoluminescence and thermal stability. CrystEngComm, 15(22), 4489-4506. https://doi.org/10.1039/c3ce40184g
Wang, Ping ; Fan, Rui Qing ; Yang, Yu Lin ; Liu, Xin Rong ; Xiao, Peng ; Li, Xin Yu ; Hasi, Wuliji ; Cao, Wen Wu. / 1-D helical chain, 2-D layered network and 3-D porous lanthanide-organic frameworks based on multiple coordination sites of benzimidazole-5,6- dicarboxylic acid : Synthesis, crystal structure, photoluminescence and thermal stability. In: CrystEngComm. 2013 ; Vol. 15, No. 22. pp. 4489-4506.
@article{27e5bdeb959742a2a57772ca387ef0f0,
title = "1-D helical chain, 2-D layered network and 3-D porous lanthanide-organic frameworks based on multiple coordination sites of benzimidazole-5,6- dicarboxylic acid: Synthesis, crystal structure, photoluminescence and thermal stability",
abstract = "One-dimensional to three-dimensional lanthanide coordination polymers 1-8 based on benzimidazole-5,6-dicarboxylic acid (H3BIDC) have been synthesized under hydrothermal conditions at different pH values, generally formulated as {[Pr(HBIDC)(ox)0.5(H2O)]·H 2O}n (1), [Yb(HBIDC)(ox)0.5(H 2O)2]n (2), and [Ln(HBIDC)(ox) 0.5(H2O)3]n [Ln = Ho (3), and Tb (4)] and {[Ln(H2BIDC)(HBIDC)(H2O)3] ·3H2O}n [Ln = Tb (5), Sm (6), Dy (7), and Gd (8), H2ox = oxalic acid]. All coordination polymers have been characterized by elemental analysis, infrared spectra and single-crystal X-ray diffraction. The structural diversity, luminescence and thermal properties of all coordination polymers have been investigated. Coordination polymers 1-8 exhibit four different structural types: topological analysis has given the 3-D pcu network, with the point symbol of {412·63} in coordination polymer 1. Coordination polymer 2 exhibits a 4-connected 4 4 topology, and coordination polymers 3-4 appear as 2-D (6,3)-connected hcb network topology. The 1-D helical infinite chain of coordination polymers 5-8 around the crystallographic 21 axis spread along the b axis direction, with different 1-D helical infinite chains forming 3-D supramolecular framework via hydrogen bonds and π-π stacking interactions. The coordination polymers 4 and 5 could be triggered to have intense characteristic lanthanide-centered green luminescence under UV excitation in the solid state at room and liquid nitrogen temperature, or dispersed in CH2Cl2 at 77 K. In coordination polymers 4 and 5, the oxalic acid introduced into coordination polymer 4 as a second ligand further sensitized the trivalent terbium ion, and resulted in longer fluorescence lifetimes of coordination polymer 4 (1058.58 μs at 298 K, 679.42 μs at 77 K in the solid-state, 867.82 μs in CH2Cl2 at 77 K) than coordination polymer 5 (595.06 μs at 298 K, 583.19 μs at 77 K in the solid-state, 584.38 μs in CH2Cl2 at 77 K). In coordination polymers 6 and 7, we not only measured emission spectra in the visible region, but also detected the infrequent NIR emission spectra in the near infrared region of samarium and dysprosium ions. The singlet excited state (30 303 cm-1) and the lowest triplet state energy level (24 390 cm-1) of H3BIDC ligand were calculated based on the UV-vis absorbance edges of ligand and the phosphorescence spectrum of Gd(iii) coordination polymer (8) at 77 K, showing that the effective extent of energy transfer from H3BIDC ligand to lanthanide ions follows the sequence of Tb3+, Dy3+ > Sm3+. Finally, thermal behaviors of all coordination polymers were studied by thermogravimetric analysis, which exhibited high thermal stability.",
author = "Ping Wang and Fan, {Rui Qing} and Yang, {Yu Lin} and Liu, {Xin Rong} and Peng Xiao and Li, {Xin Yu} and Wuliji Hasi and Cao, {Wen Wu}",
doi = "10.1039/c3ce40184g",
journal = "CrystEngComm",
publisher = "Royal Society of Chemistry",
Wang, P, Fan, RQ, Yang, YL, Liu, XR, Xiao, P, Li, XY, Hasi, W & Cao, WW 2013, '1-D helical chain, 2-D layered network and 3-D porous lanthanide-organic frameworks based on multiple coordination sites of benzimidazole-5,6- dicarboxylic acid: Synthesis, crystal structure, photoluminescence and thermal stability', CrystEngComm, vol. 15, no. 22, pp. 4489-4506. https://doi.org/10.1039/c3ce40184g
1-D helical chain, 2-D layered network and 3-D porous lanthanide-organic frameworks based on multiple coordination sites of benzimidazole-5,6- dicarboxylic acid : Synthesis, crystal structure, photoluminescence and thermal stability. / Wang, Ping; Fan, Rui Qing; Yang, Yu Lin; Liu, Xin Rong; Xiao, Peng; Li, Xin Yu; Hasi, Wuliji; Cao, Wen Wu.
In: CrystEngComm, Vol. 15, No. 22, 14.06.2013, p. 4489-4506.
T1 - 1-D helical chain, 2-D layered network and 3-D porous lanthanide-organic frameworks based on multiple coordination sites of benzimidazole-5,6- dicarboxylic acid
T2 - Synthesis, crystal structure, photoluminescence and thermal stability
AU - Wang, Ping
AU - Fan, Rui Qing
AU - Yang, Yu Lin
AU - Liu, Xin Rong
AU - Xiao, Peng
AU - Li, Xin Yu
AU - Hasi, Wuliji
AU - Cao, Wen Wu
N2 - One-dimensional to three-dimensional lanthanide coordination polymers 1-8 based on benzimidazole-5,6-dicarboxylic acid (H3BIDC) have been synthesized under hydrothermal conditions at different pH values, generally formulated as {[Pr(HBIDC)(ox)0.5(H2O)]·H 2O}n (1), [Yb(HBIDC)(ox)0.5(H 2O)2]n (2), and [Ln(HBIDC)(ox) 0.5(H2O)3]n [Ln = Ho (3), and Tb (4)] and {[Ln(H2BIDC)(HBIDC)(H2O)3] ·3H2O}n [Ln = Tb (5), Sm (6), Dy (7), and Gd (8), H2ox = oxalic acid]. All coordination polymers have been characterized by elemental analysis, infrared spectra and single-crystal X-ray diffraction. The structural diversity, luminescence and thermal properties of all coordination polymers have been investigated. Coordination polymers 1-8 exhibit four different structural types: topological analysis has given the 3-D pcu network, with the point symbol of {412·63} in coordination polymer 1. Coordination polymer 2 exhibits a 4-connected 4 4 topology, and coordination polymers 3-4 appear as 2-D (6,3)-connected hcb network topology. The 1-D helical infinite chain of coordination polymers 5-8 around the crystallographic 21 axis spread along the b axis direction, with different 1-D helical infinite chains forming 3-D supramolecular framework via hydrogen bonds and π-π stacking interactions. The coordination polymers 4 and 5 could be triggered to have intense characteristic lanthanide-centered green luminescence under UV excitation in the solid state at room and liquid nitrogen temperature, or dispersed in CH2Cl2 at 77 K. In coordination polymers 4 and 5, the oxalic acid introduced into coordination polymer 4 as a second ligand further sensitized the trivalent terbium ion, and resulted in longer fluorescence lifetimes of coordination polymer 4 (1058.58 μs at 298 K, 679.42 μs at 77 K in the solid-state, 867.82 μs in CH2Cl2 at 77 K) than coordination polymer 5 (595.06 μs at 298 K, 583.19 μs at 77 K in the solid-state, 584.38 μs in CH2Cl2 at 77 K). In coordination polymers 6 and 7, we not only measured emission spectra in the visible region, but also detected the infrequent NIR emission spectra in the near infrared region of samarium and dysprosium ions. The singlet excited state (30 303 cm-1) and the lowest triplet state energy level (24 390 cm-1) of H3BIDC ligand were calculated based on the UV-vis absorbance edges of ligand and the phosphorescence spectrum of Gd(iii) coordination polymer (8) at 77 K, showing that the effective extent of energy transfer from H3BIDC ligand to lanthanide ions follows the sequence of Tb3+, Dy3+ > Sm3+. Finally, thermal behaviors of all coordination polymers were studied by thermogravimetric analysis, which exhibited high thermal stability.
AB - One-dimensional to three-dimensional lanthanide coordination polymers 1-8 based on benzimidazole-5,6-dicarboxylic acid (H3BIDC) have been synthesized under hydrothermal conditions at different pH values, generally formulated as {[Pr(HBIDC)(ox)0.5(H2O)]·H 2O}n (1), [Yb(HBIDC)(ox)0.5(H 2O)2]n (2), and [Ln(HBIDC)(ox) 0.5(H2O)3]n [Ln = Ho (3), and Tb (4)] and {[Ln(H2BIDC)(HBIDC)(H2O)3] ·3H2O}n [Ln = Tb (5), Sm (6), Dy (7), and Gd (8), H2ox = oxalic acid]. All coordination polymers have been characterized by elemental analysis, infrared spectra and single-crystal X-ray diffraction. The structural diversity, luminescence and thermal properties of all coordination polymers have been investigated. Coordination polymers 1-8 exhibit four different structural types: topological analysis has given the 3-D pcu network, with the point symbol of {412·63} in coordination polymer 1. Coordination polymer 2 exhibits a 4-connected 4 4 topology, and coordination polymers 3-4 appear as 2-D (6,3)-connected hcb network topology. The 1-D helical infinite chain of coordination polymers 5-8 around the crystallographic 21 axis spread along the b axis direction, with different 1-D helical infinite chains forming 3-D supramolecular framework via hydrogen bonds and π-π stacking interactions. The coordination polymers 4 and 5 could be triggered to have intense characteristic lanthanide-centered green luminescence under UV excitation in the solid state at room and liquid nitrogen temperature, or dispersed in CH2Cl2 at 77 K. In coordination polymers 4 and 5, the oxalic acid introduced into coordination polymer 4 as a second ligand further sensitized the trivalent terbium ion, and resulted in longer fluorescence lifetimes of coordination polymer 4 (1058.58 μs at 298 K, 679.42 μs at 77 K in the solid-state, 867.82 μs in CH2Cl2 at 77 K) than coordination polymer 5 (595.06 μs at 298 K, 583.19 μs at 77 K in the solid-state, 584.38 μs in CH2Cl2 at 77 K). In coordination polymers 6 and 7, we not only measured emission spectra in the visible region, but also detected the infrequent NIR emission spectra in the near infrared region of samarium and dysprosium ions. The singlet excited state (30 303 cm-1) and the lowest triplet state energy level (24 390 cm-1) of H3BIDC ligand were calculated based on the UV-vis absorbance edges of ligand and the phosphorescence spectrum of Gd(iii) coordination polymer (8) at 77 K, showing that the effective extent of energy transfer from H3BIDC ligand to lanthanide ions follows the sequence of Tb3+, Dy3+ > Sm3+. Finally, thermal behaviors of all coordination polymers were studied by thermogravimetric analysis, which exhibited high thermal stability.
U2 - 10.1039/c3ce40184g
DO - 10.1039/c3ce40184g
JO - CrystEngComm
JF - CrystEngComm
Wang P, Fan RQ, Yang YL, Liu XR, Xiao P, Li XY et al. 1-D helical chain, 2-D layered network and 3-D porous lanthanide-organic frameworks based on multiple coordination sites of benzimidazole-5,6- dicarboxylic acid: Synthesis, crystal structure, photoluminescence and thermal stability. CrystEngComm. 2013 Jun 14;15(22):4489-4506. https://doi.org/10.1039/c3ce40184g